View
7
Download
0
Category
Preview:
Citation preview
By Dong Wang
Huntsman Advanced Materials
Benzoxazine Resin for Aerospace Interior Applications
Advanced Materials Advanced Materials
Outline
Background and challenges
Huntsman ADMAT product-line and benzoxazine technology overview
Benzoxazine resin for transportation interior application
− Resin chemistry comparison to traditional phenolic resin
− XU 35710 FST neat resin properties
− XU 35710 FST composite laminate properties
− XU 35710 FST resin for pre-pregging process
Summary
Disclaimer
Advanced Materials Advanced Materials
Background and Challenges
Examples of Aerospace interior applications
− Liners
− Ceilings
− Floor panels
− Overhead bins
− Bulkheads
Phenolic resin laminate for aerospace interior applications
− Low cost
− Excellent FST performance
Advanced Materials Advanced Materials
Background and Challenges
Main issues of using traditional phenolic resin
Volatile release
during curing
EHS concerns
Long manufacturing
cycle time
Low mechanical
performances
Laminate quality
control difficulty
Other issues of using traditional phenolic resin
− Poor storage stability
− Typically solvent based
Advanced Materials Advanced Materials
Background and Challenges
Ideal target of next generation resin for interior application
Performance:
− Comparable FST performance
− Improved laminate mechanical performance
− Improved storage stability
Processing:
− Low volatile release curing
− Short manufacturing cycle time
− Easy laminate quality control
− Processible by liquid molding (RTM, VARTM, RFI, etc)
Others:
− Comparable cost
Advanced Materials Advanced Materials
Base Resins Specialty Components Formulations
Curing Agents Multifunctionals
Matting agents Crosslinkers
Reactive Diluents
BisF/EPN/ECN
Waterbornes Reactive PAA
Adhesives Encapsulation
Tooling Insulation
Composites Protection
Liquid epoxy resins
Solid epoxy resins
Epoxy solutions
Laminates
Huntsman Advanced Materials ― Our Products
Advanced Materials Advanced Materials
High-Performance Building Blocks for Advanced Composites
■ Liquid & Solid Bis-A Epoxies
■ Bis-F Epoxies
■ EPNs
■ ECNs
■ Reactive Epoxy Diluents
■ Brominated Bis-A Epoxy
■ Toughened Epoxies
■ Cycloaliphatic Epoxies
■ Specialty Multifunctional Epoxies –
Liquids & Solids
■ Bismaleimides / Polyimides
■ Polyamide-Imide
■ Cyanate Esters
■ Aliphatic Amine
■ Cycloaliphatic Amine
■ Polyamides
■ Phenalkamines
■ Aromatic Amines
■ Anhydride
■ Accelerators
■ Specialty Latent Hardeners
Curing Agents
Chemistry Offered by Huntsman Advanced Material
Advanced Materials Advanced Materials
High-Performance Building Blocks for Advanced Composites
Product Families Features
Multifunctionals Araldite® MY 720 Family Liquid, easy processing, high Tg
Araldite® MY 0500 Family Low-viscosity liquid, high Tg
Araldite® MY 0600 Family Liquid, high modulus, high Tg
Other / Misc Araldite® MY 0816 Low-viscosity liquid, high toughness
Tactix® 742 High Tg, high thermal stability
Tactix® 556 / 756 High moisture resistance, high Tg
Novolac Resins Araldite® Epoxy Phenol Novolacs (EPNs) Chemical & heat resistance
Araldite® Epoxy Cresol Novolacs (ECNs) Chemical & heat resistance
Bismaleimides Matrimid® 5292 A/B Very high temperature resistance (above
300ºC), good water & chemical resistance
Curing Agents Aradur® 9664-1 / 976-1 High Tg, high modulus, good chemical and
thermal resistance
Aradur® 9719-1 High modulus, high toughness
Typical Product Offered by Huntsman Advanced Material
Advanced Materials Advanced Materials
S
N
O O
N
CH3
CH3
O O
NN
CH
2
O O
NN
N
O
N
O
O
O N
O O
N
Thiodiphenol-based
Benzoxazine
Bisphenol A-based
Benzoxazine
Bisphenol F-based
Benzoxazine
Dicyclopentadiene-based
Benzoxazine
Phenolphthalein-based
Benzoxazine
NO
R
Mono-phenol-based
Benzoxazine
Huntsman Benzoxazine Technology
Advanced Materials
Product Advantages/Benefits Potential Application
XU35610 (BPA)
• Good solvent solubility • Volatile/void free during curing • High Tg/modulus
• Aerospace structural • High temp tooling
Araldite® MT 35700 (BPF)
• High-Tg/modulus • Good chemical resistance • Good flammability properties
• Aerospace structural • Transportation interior • High temp tooling
XU35710 FST
• Good FST • Low viscosity • Low temperature (350F) curing • Low cost • High Modulus/tough-ness
• Aerospace and other transportation interior • Industrial composite (auto, down-hole, etc.) • FST tooling
XU 35910 (Thiodiphenol)
• Low viscosity • Low temperature (350F) curing • High Tg/ modulus
• Aerospace structural • Industrial composite (auto, down-hole, etc.) • High temp tooling
XU 35500 (Cardanol)
• Liquid • Green chemistry
• Viscosity diluent for Box formulation in various applications • Industrial composite building-block (auto, down-hole, etc)
DT 300 / DT 310 • White crystals • Catalysts used to lower cure temperature or shorten cure cycle. Suitable for Benzoxazines or BOX/Epoxy blends
Benzoxazine Products for Composites Application
Advanced Materials Advanced Materials
Benzoxazine for Interior Application
Main advantages of benzoxazine resins (for interior application)
− High modulus
− Low water absorption / moisture pick-up
− High Tg/thermal performance
− Good flame retardant properties
− Low curing shrinkage
− Good electrical properties
− No volatile release during cure
− Storage stable at room temperature
− Cost-effective
Promising candidate to replace phenolic resin for interior application !
Advanced Materials Advanced Materials
Resin Chemistry Comparison
Traditional Resole Synthesis
− Poor storage stability due to high reactivity of methylol groups,
Gardziella, A.; Pilato, L. A.; Knop, A., “Phenolic Resins: Chemistry, Application, Standardization, Safety and Ecology”, Springe, 1999
Advanced Materials Advanced Materials
OH
R
CH2OH
CH2OH2
OH
CH2 O CH2
R
CH2OH
OH
R
CH2OH
OH
CH2
R
CH2OH
OH
CH2OH
R
+ H2O
+ H2O + CH2O
Resin Chemistry Comparison
Traditional Resole Curing
− Water and formaldehyde released
Gardziella, A.; Pilato, L. A.; Knop, A., “Phenolic Resins: Chemistry, Application, Standardization, Safety and Ecology”, Springe, 1999
Advanced Materials Advanced Materials
Benzoxazine Synthesis
− Water removed before curing
− Ring structure instead of reactive methylol group, better storage stability
− Lower viscosity due to monomeric ring structure
− Amine is used beside phenol and formaldehyde as raw material
Resin Chemistry Comparison
Advanced Materials Advanced Materials
Benzoxazine Curing
− Ring opening mechanism
− No extra volatile release due to water pre-removal
− Low void content in resin/laminate
− Higher aromatic content retained , comparable FST
− Nitrogen element could further contribute to FST properties
NO
R1
R2OH
N
R1
OH
R1
R2nn
Resin Chemistry Comparison
Advanced Materials Advanced Materials
XU 35710 FST
Physical Form Amber viscous liquid
Total Solid* >99%
Viscosity at 100 oC (cps) 30-100 cps
Gelling time at 200 oC (sec) 300-450
XU 35710 FST Product Characteristics
Neat Resin Properties
Advanced Materials Advanced Materials
XU 35710 FST Processing Characteristics
− The product has a low viscosity compared to typical BPA or BPF
benzoxazines, and provides better processability and easier resin handling
Neat Resin Properties
Advanced Materials Advanced Materials
XU 35710 FST Processing Characteristics
− Long pot-life for liquid molding application
Neat Resin Properties
Advanced Materials Advanced Materials
XU 35710 FST Reactivity
Neat Resin Properties
Advanced Materials Advanced Materials
XU 35710 FST Curing Characteristics
− Volatile/void free during curing
Dish casting results with no pre-degassing
Neat Resin Properties
Advanced Materials Advanced Materials
Properties
XU 35710 FST
Flexural strength, Mpa 121
Flexural modulus, Gpa 5.2
Flexural ultimate elongation, % 2.3
Tensile strength, Mpa 60
Tensile modulus, Gpa 4.9
Tensile ultimate elongation, % 1.3
K1C, Mpa ·m0.5 0.92
G 1C, J/m2 200
Physical Properties of XU 35710 FST Neat Resin
− Cured resin shows high modulus, high strength, and high toughness
Neat Resin Properties
Advanced Materials Advanced Materials
Laminate Properties by RTM
Test Method Specification XU 35710 Benzoxazine
Flammability – 60 second vertical
burn
Extinguish Time –
Burn Length –
Drip Extinguish Time -
FAR 25.853(a)
< 15 seconds
< 6 inches
< 3 seconds
0.0
3.7
0.0
Smoke Density
Specific Optical Density -
FAR 25.853(d)
< 200 (Ds)
11
Heat release
Total Heat Release –
Peak Heat Release-
FAR 25.853(d)
< 65 kW.min /m2
< 65 kW/m2.
18
29
Toxicity BSS 7239 HCN – <150.
CO – Ref.
NOx – <100.
SO2 – <100.
HF – <200.
HCL – <500.
2
19
3
0
1
0
FST Properties of 2 ply XU 35710 FST/7781 Glass Laminate by RTM
*: 50% fiber volume
*: curing condition: 2h@150 oC +2h@180 oC
Advanced Materials Advanced Materials
Properties Method XU 35710 FST Typical Aero
Phenolic
Flexural modulus (warp), Gpa ISO178
27 20-24
Flexural strength (warp), MPa 663 470-550
Tensile modulus (warp), GPa
ISO527
28 19-24
Tensile strength (warp), MPa 457 380-400
ILSS (warp), MPa ISO14130 50 24-50
Compression modulus (warp), GPa
ISO14126
29 20-24
Compression strength (warp), MPa 555 350-380
Laminate Properties by RTM
Mechanical Properties of XU 35710 FST/7781 Glass Laminate
*: 50% fiber volume
*: curing condition: 2h@150 oC +2h@180 oC
Advanced Materials Advanced Materials
Increase XU 35710 FST Reactivity for Low Temperature Cure
XU 35710 FST 100 100
Novolac SD-1702* 0 20
DSC onset/peak temperature, oC 215/227 174/202
Curing profile 300 oF/1h +350 oF/ 90min 320 oF/1h
Tg, oC 137 / 142 (re-run) 127/143(re-run)
*: From Momentive Specialty Chemical
XU 35710 FST for Prepregging Process
Advanced Materials Advanced Materials
XU 35710 FST for Prepregging Process
Formulation System # #1 #2 #3
DSC reactivity onset/peak, °C 150/188 117/183 127/183
Solvent prepregging condition: 130 °C (265 oF) /3min
Drape Good Good OK
Press curing condition: 130°C (265 oF) /90min at 20psi
Tg by DSC, °C 102 109 117
Tg by DMA (E’), °C 115 123 129
Press curing condition: 145°C (293 oF) /60min at 20psi
Tg by DSC, °C 121 134 127
Tg by DMA (E’), °C 129 134 139
Post cured at 160 °C/1h
Tg by DSC, °C 137 147 138
Tg by DMA (E’), °C 138 138 144
− Resin formulations based on XU 35710 FST show good Tg build-up and are curable
with temperature as low as 130 oC (266 oF)
XU 35710 FST Based Formulation for Solvent Prepregging Process
Advanced Materials Advanced Materials
XU 35710 FST for Prepregging Process
Rheology Profile of XU 35710 FST Based Formulation for Prepregging Process
Advanced Materials Advanced Materials
XU 35710 FST for Prepregging Process
Formulation Test Method Specification Formulation #1 Formulation #2 Formulation #3
Curing condition 145 oC (293 oF) /1h
Fibre volume content, % 55 52 50
Flammability – 60 second vertical burn
Extinguish Time –
Burn Length –
Drip Extinguish Time -
FAR 25.853(a)
< 15 seconds
< 6 inches
< 3 seconds
0.0
4.3
0.0
0.0
5.5
0.0
0.0
5.2
0.0
Smoke Density
Specific Optical Density -
FAR 25.853(d)
< 200 (Ds)
9.2
8.3
14.5
Heat release
Total Heat Release –
Peak Heat Release-
FAR 25.853(d)
< 65 kW.min /m2
< 65 kW/m2
22
46
38
51
30
41
Toxicity BSS 7239 HCN – <150. CO – Ref. NOx – <100. SO2 – <100. HF – <200. HCL – <500.
<5 45 8
<5 <5 <5
<5 101 11 <5 <5 <5
<5 56 7
<5 <5 <5
Advanced Materials Advanced Materials
Summary
New cost-effective benzoxazine building block XU 35710 FST has been developed and evaluated for aerospace and other transportation interior applications.
The new resin demonstrates a series of advantages over traditional phenolic resin with comparable FST performances
− Volatile/void free during cure
− Improved resin modulus, strength and toughness
− Improved laminate mechanical performances
− Shorter manufacturing cycle time
− Better storage stability
− Easy to process by RTM or other liquid molding techniques with its low viscosity and long pot-life
The new resin also fits traditional solvent or hot-melt prepreg process with three formulation demonstrated. The formulated systems demonstrate good rheology control and low temperature cure characteristics, while still keep good FST performances.
With its performance and processing advantages, the resin could also be used by itself or with further formulation for other aerospace and industrial composite applications.
Advanced Materials Advanced Materials
Disclaimer
The slides following hereafter contain information that is confidential and proprietary to Huntsman Corporation, and/or its appropriate affiliate(s) (“Huntsman”) Recipients of this presentation and the information contained herein shall not copy or replicate the same by any means whatsoever and shall not share or show such information to third patties..
While the information contained herein is, to the best of Huntsman’s knowledge, accurate as of the date of its presentation, it is the responsibility of recipients to determine the applicability and/or suitability of such information for their own particular purpose Huntsman accepts no responsibility for any damages of any kind incurred by recipient and/or third patties resulting from the use of, reliance upon, or the misuse of such information for any purpose.
All information contained herein is provided “as is” without any warranties, express or implied, and under no circumstances shall the authors or Huntsman be liable for any damages of any nature whatsoever resulting from the use or reliance upon such information. Nothing contained in this publication should be construed as a license under any intellectual property right of any entity, or as a suggestion, recommendation, or authorization to take any action that would infringe any patent. The term “Huntsman” is used herein for convenience only, and refers to Huntsman Corporation, its direct and indirect affiliates, and their employees, officers, and directors
Recommended